CN105670207B - A kind of electronic cigarette shell of lightweight antibacterial and preparation method thereof - Google Patents

Abstract

The invention discloses a kind of electronic cigarette shells of lightweight antibacterial and preparation method thereof.During polymer is kneaded, nucleating agent, foaming agent, blowing promotor and toughener are added into, the foaming in tubular die, the polymer pipe to be foamed obtains the shell of the electronic cigarette of certain length by cutting.Electronic cigarette shell produced by the present invention can effectively reduce the weight of electronic cigarette, and the nano-ZnO used in blowing promotor has hollow porous structure, can generate more active oxygens and active zinc ions to achieve the effect that inhibit bacteria.The preparation method raw material of the present invention is easy to get, and synthesis step is simple, the electronic cigarette shell of available lightweight antibacterial.

Description

A light antibacterial electronic cigarette case and preparation method thereof

technical field

The invention belongs to the technical field of composite materials, and in particular relates to a lightweight antibacterial electronic cigarette casing and a preparation method thereof.

Background technique

E-cigarettes are electronic products that imitate traditional cigarettes and have the same appearance, smoke, taste and sensation as cigarettes. However, there are batteries and pods in the electronic cigarette, and it is wrapped by hard materials (such as metal, hard plastic, etc.) , which will largely affect consumers' sensory evaluation of e-cigarettes. Therefore, how to reduce the weight of electronic cigarettes is also a difficult problem in electronic cigarette technology.

In order to reduce the weight of plastic parts with the same volume, the method of foaming can be used to add certain non-toxic and harmless gas to the plastic parts to reduce the density of the plastic parts, and finally achieve the reduction of the weight of the plastic parts. In the preparation of foamed polymer materials, microcellular foaming and structural foaming can be used, and different foaming methods can be selected according to the properties of different polymers. Generally, the apparent density of the polymer can be reduced to 50% to 80% of the original. %. And, because the foamed polymer material obtained has a dense surface layer and a microporous structure inside, its strength per unit mass and impact resistance are higher than those of the same kind of unfoamed material, so it can also be used in weight loss while reducing weight. To a certain extent, the mechanical properties of the material are improved.

In addition, in the blending of polymer foaming materials, it is necessary to add certain foaming aids (nucleating aids) ZnO and TiO ₂ , these nanoscale oxides have certain antibacterial ability, which has been widely reported . Therefore, while the nano-ZnO is uniformly dispersed in the polymer resin to help the nucleation and foaming, it can also play an antibacterial effect in the final polymer material. However, the surface of ZnO nanoparticles reported in the past is bare after the preparation is completed (stabilizers disappear after high temperature calcination), so the dispersion in water or polymers is very poor, and further modification is required. Excessive modification may lead to a decrease in the ability of the surface of ZnO nanoparticles to receive light, and the antibacterial mechanism cannot be well exerted. It has recently been proposed that the preparation of ZnO by the hydrothermal method can directly dehydrate and form ZnO nanoparticles under high temperature hydrothermal action without calcination, so that the components of the destabilizer can be better preserved. On the other hand, it has also been reported that nanoparticles with a hierarchical structure can better absorb and convert light, so the preparation of ZnO with a special structure can enhance its antibacterial effect.

Considering that electronic cigarettes need to be used multiple times, the requirements for antibacterial performance are also high. Therefore, the foamed polymer resin obtained by injection molding with nano-ZnO with a special structure as a foaming aid can not only effectively reduce the weight of electronic cigarettes, but also achieve antibacterial effects. It is a light antibacterial electronic cigarette. Method for preparing smoke casing.

Contents of the invention

The purpose of the present invention is to provide a method for preparing a lightweight aseptic electronic cigarette casing. The lightweight sterile electronic cigarette casing is specifically a foamed polymer tube mixed with hollow porous nano-ZnO powder. By using PAA and other cross-linked polymers containing a large number of carboxyl groups as templates, Zn ²⁺ is complexed, and under high pressure and high pressure, it reacts with ^OH- generated by hydrolysis of amines such as urea to generate Zn in situ on PAA. (OH) ₂ , and continued to dehydrate under this condition to form crystalline ZnO, forming a shell on the surface of PAA; during the formation of ZnO, under the action of strong alkali and high temperature, the internal PAA decomposed and cross-linked to form PAA chains , ran out from the ZnO shell, and complexed on the surface of ZnO, became a stabilizer of ZnO, and vacated the middle shell, and generated wall holes. Such hollow porous ZnO is used as a foaming aid and antibacterial agent for foamed plastics. It not only has a light apparent density that helps reduce the weight of the plastic, but also gives a large specific surface area for light absorption and color refraction inside the particle. Inhibit the growth of bacteria by producing active oxygen or active zinc ions.

On the other hand, in order to ensure that the original performance of the original polymer shell is not affected, such as good impact resistance, strong heat resistance, good corrosion resistance, insulation, heat insulation performance, etc., the foaming amount used in the present invention Moderate, can produce a sufficient amount of microbubbles in the polymer material, not only can ensure its original performance but also enhance some of its performance to a certain extent. However, the amount of foaming should not be too large. Excessive foaming amount will make the polymer brittle and brittle, and the performance of the polymer will be greatly reduced. Finally, the obtained foamed polymer tube can be cut into electronic cigarette shells according to the specifications of electronic cigarettes.

The purpose of the present invention is to provide a lightweight aseptic electronic cigarette casing and its preparation method

A method for preparing a lightweight antibacterial electronic cigarette case of the present invention comprises the following steps:

Step 1, disperse 0.1-5 parts by weight of cross-linked polyacrylic acid PAA or cross-linked polymethacrylic acid PMAA in 25-500 parts by weight of deionized water, add 0.1-2.5 parts by weight of soluble zinc salt and amine compounds 0.4-8 parts by weight, stir and dissolve to obtain a reaction system; transfer the reaction system to a stainless steel high-pressure reactor, seal it well and transfer it to an oven, and react at 120-200°C for 12-36 hours; lower the reactor to room temperature , centrifuge at a speed of 5000-12000 rpm for 2-10 minutes to separate hollow porous ZnO, wash with deionized water for 3-5 times, and dry at 40-60°C for 24 hours to obtain hollow porous nano-ZnO powder;

Step 2, 1-5 parts by weight of porous hollow nano-ZnO powder, 80-100 parts by weight of polymer masterbatch, 5-10 parts by weight of modification aid, 1-3 parts by weight of calcium carbonate and 1-4 parts by weight of The foaming agent is added to the kneader, heated and kneaded for 1-5 hours, and then added to the mixer; in the mixer, it is quickly injected into the tubular mold through high pressure, and the molding pressure is 2-7MPa, and the temperature is 50-80℃. Under the low-pressure foaming method, the polymer melt is foamed and molded; the molded shell is cooled and released from the mold, and after drying, a foamed aseptic tube is obtained, and the tube is cut to obtain a light antibacterial electronic cigarette shell.

As a further improvement, the cross-linked PAA or cross-linked PMAA is prepared by distillation precipitation polymerization; the cross-linking agent used is a bis-vinyl bis-acrylamide cross-linking agent, a bis-vinyl diester cross-linking agent agent or divinylbenzene crosslinking agent.

As a further improvement, the cross-linked polyacrylic acid PAA or the cross-linked polymethacrylic acid PMAA has a particle diameter of 50-500 nm, and a cross-linking degree of 10%-50%.

As a further improvement, in the first step, cross-linked PAA is used.

As a further improvement, in the first step, the soluble zinc salt is ZnCl ₂ , Zn(NO ₃ ) ₂ , ZnSO ₄ or zinc acetate.

As a further improvement, in the first step, the amine compounds are urea, hexamethylene tetraammonium, hydrazine hydrate, ethanolamine, diethanolamine and melamine.

As a further improvement, in the second step, the polymer masterbatch is PC resin, ABS resin or a mixture of both.

As a further improvement, in the step 2, the modifying auxiliary agent is composed of 5-20 parts by weight of antioxidant, 0-30 parts by weight of foaming auxiliary agent and 20-80 parts by weight of toughening agent, wherein The toughening agent is one or a mixture of SBS, SEBS and EVA; the foaming aid is TiO ₂ or a mixture of TiO ₂ and ZnO; the antioxidant is quinoline derivatives and phosphite derivatives.

As a further improvement, the foaming agent in the second step is a master batch ball of azo compound, nitroso compound or sodium carbonate encapsulated by a polymer carrier resin.

Compared with the original polymer pipe, the relative density of the lightweight aseptic foamed polymer pipe obtained by the invention is reduced by 10% to 60%.

The present invention prepares hollow porous ZnO nanoparticles by means of hydrothermal method, which can save the process of high segmental sintering and reduce the sintering between particles; core PAA decrosslinking not only forms a hollow structure for ZnO particles in situ , the released PAA chain can also be a stabilizer of ZnO, so that its dispersion in the polymer is further improved, and no coupling agent is used to modify it.

The raw material for preparing a light-weight aseptic foaming polymer pipe is easy to obtain, and the synthesis steps are simple, and the preparation of a light-weight and antibacterial electronic cigarette casing will have broad market application prospects.

Compared with prior art, the advantage of the present invention is:

1. The hollow porous ZnO produced in the present invention is used as a foaming aid and an antibacterial agent for foamed plastics, which not only helps to reduce the weight of plastics by being light in apparent density, but also provides a large specific surface area for the absorption of light And color refraction inside the particles to generate active oxygen or active zinc ions to inhibit the growth of bacteria.

2. In order to ensure that the original performance of the original polymer shell is not affected, such as good impact resistance, strong heat resistance, good corrosion resistance, insulation, heat insulation performance, etc., the foaming amount used in the present invention is moderate, A sufficient amount of microbubbles can be produced in the polymer material, which can not only ensure its original performance, but also enhance some of its performance to a certain extent. However, the amount of foaming should not be too large. Excessive foaming amount will make the polymer brittle and brittle, and the performance of the polymer will be greatly reduced. Finally, the obtained foamed polymer tube can be cut into electronic cigarette shells according to the specifications of electronic cigarettes.

3. Compared with the original polymer pipe, the relative density of the lightweight aseptic foamed polymer pipe obtained by the present invention is reduced by 10% to 60%. The present invention prepares hollow porous ZnO nanoparticles by means of hydrothermal method, which can save the process of high segmental sintering and reduce the sintering between particles; core PAA decrosslinking not only forms a hollow structure for ZnO particles in situ , the released PAA chain can also be a stabilizer of ZnO, so that its dispersion in the polymer is further improved, and no coupling agent is used to modify it.

4. The raw materials for preparing a light-weight aseptic foamed polymer pipe in the present invention are easy to obtain, and the synthesis steps are simple. It will have a broad market application prospect for the preparation of a light-weight antibacterial electronic cigarette casing.

Description of drawings

Fig. 1 is the schematic diagram of the preparation process of hollow porous ZnO nanoparticles;

Fig. 2 is the scanning electron micrograph of hollow porous ZnO nanoparticle in embodiment 1-7;

FIG. 3 is a transmission electron microscope image of a single hollow porous ZnO nanoparticle in Examples 1-7.

Detailed ways

In order to enable those skilled in the art to better understand the technical solutions of the present invention, and to make the above-mentioned features, purposes and advantages of the present invention clearer and easier to understand, the present invention will now be further explained in conjunction with the embodiments. It should be noted that, here All examples listed are illustrative only and are not meant to limit the scope of the invention. The materials and instruments used in the examples are all commercially available products. The foaming agent used in the embodiment is a master batch ball encapsulated by azo compound, nitroso compound or sodium carbonate through polymer carrier resin. Cross-linked PAA or cross-linked PMAA are prepared by distillation precipitation polymerization; the cross-linking agent used is bis-vinyl bis-acrylamide cross-linking agent, bis-vinyl diester cross-linking agent or bis-vinylbenzene Class cross-linking agent; the antioxidants used are commercialized antioxidants, and their trade names are respectively antioxidant 1010, antioxidant 1076 and antioxidant 168, and their active ingredients are quinoline derivatives or phosphite derivatives .

Figure 1 is a schematic diagram of the preparation process of hollow porous ZnO nanoparticles: 1. In a deionized water system where polyacrylic acid microspheres, zinc salts, and urea co-exist with a large number of carboxyl groups on the surface, under the action of high temperature, amines such as urea are first Hydrolysis produces an alkaline environment so that the zinc salt forms zinc hydroxide, and attaches to the negatively charged polyacrylic acid microspheres with carboxyl groups in fine particles to form a shell, that is, the core-shell structure microspheres of polyacrylic acid@zinc hydroxide; 2. As the reaction continues, the zinc hydroxide layer on the surface gradually becomes thicker, and the high temperature and strong alkali environment generated can slowly hydrolyze the polyacrylic acid microspheres inside, that is, polyacrylic acid with a larger shell layer and a divergent core is formed @ Hydroxide Zinc core-shell structure microspheres; 3. The zinc hydroxide layer on the final surface is dehydrated and crystallized under high-temperature hydrothermal conditions to form zinc oxide, while the polyacrylic acid microspheres in the middle are completely degraded and dissolved in water to leave a cavity, and finally Zinc oxide hollow particles are formed.

Example 1:

Use 0.5g of cross-linked polyacrylic acid PAA (particle size: 150nm, cross-linking degree: 25%) as a template, disperse in 200mL of deionized water, finally add ZnCl ₂ 0.5g and urea 1.0g, and stir evenly to make it completely Dissolve in water. The whole system was transferred to the tetrafluoroethylene liner (volume 300mL) of a stainless steel autoclave, sealed well, then transferred to an oven, and heated to 120°C for 36 hours. After the reaction, the reaction kettle was lowered to room temperature, and the obtained hollow porous ZnO was separated by centrifugation (5000rpm for 10min), washed 5 times with deionized water, and dried at 60°C for one day by vacuum drying. The hollow porous nanometer ZnO powder is obtained.

5 parts by weight of antioxidant 1010, 10 parts by weight of TiO ₂ foaming aid and 30 parts by weight of SBS were mixed to make a modification aid. Then add 86 parts of ABS masterbatch, 7 parts of modifying additives, 3 parts of porous hollow nano-ZnO powder, 3 parts of calcium carbonate and 1 part of foaming agent into the kneader, heat and knead for 5 hours, and then add them into the kneader. In the mixing machine, it is injected into the tubular mold through high-pressure rapid injection, and the polymer melt is foam-molded at a molding pressure of 7MPa and a temperature of 80°C by using a low-pressure foaming method. Finally, the molded shell is cooled and released from the mold, and after drying, a foamed aseptic tube is obtained. After the tube is cut, a lightweight and antibacterial electronic cigarette casing can be obtained. A light-weight aseptic electronic cigarette shell with 1% foaming agent added and 3% nano-ZnO added is prepared, and its weight is reduced by 22% compared with the original pipe (without adding foaming agent). Fig. 2 is a scanning electron microscope image of hollow porous ZnO nanoparticles; Fig. 3 is a transmission electron microscope image of a single hollow porous ZnO nanoparticle.

Example 2:

Refer to Example 1 for the preparation method of the hollow porous nano-ZnO powder.

The modification auxiliary agent is prepared by mixing 20 parts by weight of antioxidant 1076, 15 parts by weight of TiO ₂ , 15 parts by weight of ZnO and 20 parts by weight of SEBS. Add 85 parts of ABS masterbatch, 7 parts of modification additives, 3 parts of porous hollow nano-ZnO powder, 3 parts of calcium carbonate and 2 parts of foaming agent into the kneader, heat and knead for 1 hour, and then add them into the kneader. In the mixing machine, it is injected into the tubular mold through high-pressure rapid injection, and the polymer melt is foam-molded at a molding pressure of 2 MPa and a temperature of 50 ° C by using a low-pressure foaming method. Finally, the molded shell is cooled and released from the mold, and after drying, a foamed aseptic tube is obtained. After the tube is cut, a lightweight and antibacterial electronic cigarette casing can be obtained. A lightweight aseptic electronic cigarette casing with 2% foaming agent added and 3% nano-ZnO added is prepared, and its weight is reduced by 37% compared with the original pipe (without adding foaming agent).

Example 3:

Refer to Example 1 for the preparation method of the hollow porous nano-ZnO powder.

Mix 5 parts by weight of antioxidant 1076, 20 parts by weight of TiO ₂ and 80 parts by weight of EVA to make a modification aid. Add 84 parts of ABS masterbatch, 7 parts of modification additives, 3 parts of porous hollow nano-ZnO powder, 3 parts of calcium carbonate and 3 parts of foaming agent into the kneader, heat and knead for 3 hours, and then add them into the kneader. In the mixing machine, it is injected into the tubular mold through high-pressure rapid injection, and the polymer melt is foam-molded at a molding pressure of 5 MPa and a temperature of 70 ° C by using a low-pressure foaming method. Finally, the molded shell is cooled and released from the mold, and after drying, a foamed aseptic tube is obtained. After the tube is cut, a lightweight and antibacterial electronic cigarette casing can be obtained. A lightweight aseptic electronic cigarette casing with 3% foaming agent added and 3% nano-ZnO added is prepared, and its weight is reduced by 53% compared with the original pipe (without adding foaming agent).

Example 4:

Refer to Example 1 for the preparation method of the hollow porous nano-ZnO powder.

The modified auxiliary agent is prepared by mixing 10 parts by weight of antioxidant 1076, 15 parts by weight of TiO ₂ , 20 parts by weight of SBS, and 20 parts by weight of SEBS. Add 87 parts of ABS masterbatch, 7 parts of modified additives, 1 part of porous hollow nano-ZnO powder, 3 parts of calcium carbonate and 2 parts of foaming agent into the kneader, heat and knead for 1 hour, and then add it to the kneader. In the mixing machine, it is injected into the tubular mold through high-pressure rapid injection, and the polymer melt is foam-molded at a molding pressure of 7MPa and a temperature of 80°C by using a low-pressure foaming method. Finally, the molded shell is cooled and released from the mold, and after drying, a foamed aseptic tube is obtained. After the tube is cut, a lightweight and antibacterial electronic cigarette casing can be obtained. A lightweight aseptic electronic cigarette casing with 2% foaming agent added and 1% nano-ZnO added is prepared, and its weight is reduced by 30% compared with the original pipe (without adding foaming agent).

Example 5:

Refer to Example 1 for the preparation method of the hollow porous nano-ZnO powder.

Mix 10 parts by weight of antioxidant 1010, 10 parts by weight of phosphite derivatives, and 40 parts by weight of SBS to prepare a modification aid. Add 83 parts of ABS masterbatch, 7 parts of modification additives, 5 parts of porous hollow nano-ZnO powder, 3 parts of calcium carbonate and 2 parts of foaming agent into the kneader, heat and knead for 1 hour, and then add them to the kneader. In the mixing machine, it is injected into the tubular mold through high-pressure rapid injection, and the polymer melt is foamed at a molding pressure of 7 MPa and a temperature of 60 ° C by using a low-pressure foaming method. Finally, the molded shell is cooled and released from the mold, and after drying, a foamed aseptic tube is obtained. After the tube is cut, a lightweight and antibacterial electronic cigarette casing can be obtained. A lightweight aseptic electronic cigarette shell with 2% foaming agent added and 5% nano-ZnO added is prepared, and its weight is reduced by 43% compared with the original pipe (without adding foaming agent).

Embodiment 6:

Refer to Example 1 for the preparation method of the hollow porous nano-ZnO powder.

Mix 10 parts by weight of antioxidant 1010, 15 parts by weight of TiO ₂ foaming aid and 30 parts by weight of SBS to make a modification aid. Add 85 parts of PC masterbatch, 7 parts of modification additives, 3 parts of porous hollow nano-ZnO powder, 3 parts of calcium carbonate and 2 parts of foaming agent into the kneader, heat and knead for 4 hours, and then add them to the kneader. In the mixing machine, it is injected into the tubular mold through high-pressure rapid injection, and the polymer melt is foam-molded at a molding pressure of 6 MPa and a temperature of 70 ° C by using a low-pressure foaming method. Finally, the molded shell is cooled and released from the mold, and after drying, a foamed aseptic tube is obtained. After the tube is cut, a lightweight and antibacterial electronic cigarette casing can be obtained. A lightweight aseptic electronic cigarette casing with 2% foaming agent added and 3% nano-ZnO added is prepared, and its weight is reduced by 31% compared with the original pipe (without adding foaming agent).

Embodiment 7:

Refer to Example 1 for the preparation method of the hollow porous nano-ZnO powder.

Mix 10 parts by weight of antioxidant 1010, 15 parts by weight of TiO ₂ foaming aid and 30 parts by weight of SBS to make a modification aid. Add 42 parts of PC masterbatch, 43 parts of ABS masterbatch, 7 parts of modification additives, 3 parts of porous hollow nano-ZnO powder, 3 parts of calcium carbonate and 2 parts of foaming agent into the kneader, heat and knead for 3 hours, then add into the mixer. In the mixing machine, it is injected into the tubular mold through high-pressure rapid injection, and the polymer melt is foam-molded at a molding pressure of 5 MPa and a temperature of 40 ° C by using a low-pressure foaming method. Finally, the molded shell is cooled and released from the mold, and after drying, a foamed aseptic tube is obtained. After the tube is cut, a lightweight and antibacterial electronic cigarette casing can be obtained. A lightweight aseptic electronic cigarette casing with 2% foaming agent added and 3% nano-ZnO added is prepared, and its weight is reduced by 35% compared with the original pipe (without adding foaming agent).

Embodiment 8:

Take 0.5g of cross-linked polyacrylic acid PAA (particle size: 150nm, cross-linking degree: 25%) as a template, disperse in 200mL of deionized water, finally add Zn(NO ₃ ) ₂ 0.5g and urea 1.0g, and mix well Stir to completely dissolve in water. The entire system was transferred to a tetrafluoroethylene liner (volume 300 mL) of a stainless steel autoclave, sealed well, then transferred to an oven, and heated to 200°C for 12 hours. After the reaction, the reaction kettle was lowered to room temperature, and the obtained hollow porous ZnO was separated by centrifugation (12,000 rpm for 2 min), washed with deionized water three times, and dried at 40° C. for one day by vacuum drying. The hollow porous nanometer ZnO powder is obtained. The prepared hollow porous ZnO nanoparticles have an outer diameter of 560 nm.

For the process route of kneading and extruding into a tube, refer to Example 2 to obtain a lightweight and antibacterial electronic cigarette casing.

Embodiment 9:

Take 0.5g cross-linked polyacrylic acid PAA (particle size is 150nm, cross-linking degree is 25%) as a template, disperse in 200mL deionized water, finally add ZnSO ₄ 0.5g and urea 1.0g, and stir evenly to make it completely Dissolve in water. The whole system was transferred to the tetrafluoroethylene liner (volume 300mL) of a stainless steel autoclave, sealed well, then transferred to an oven, and heated to 120°C for 36 hours. After the reaction, the reaction kettle was lowered to room temperature, and the obtained hollow porous ZnO was separated by centrifugation (5000rpm centrifugation for 7min), washed three times with deionized water, and dried at 60°C for one day by vacuum drying. The hollow porous nanometer ZnO powder is obtained. The prepared hollow porous ZnO nanoparticles have an outer diameter of 490 nm.

For the process route of kneading and extruding into a tube, refer to Example 2 to obtain a lightweight and antibacterial electronic cigarette casing.

Example 10:

Use 0.5g of cross-linked polyacrylic acid PAA (particle size: 150nm, cross-linking degree: 25%) as a template, disperse in 200mL of deionized water, finally add 0.5g of zinc acetate and 1.0g of urea, and stir evenly to make it completely Dissolve in water. The entire system was transferred to a tetrafluoroethylene liner (volume 300 mL) of a stainless steel autoclave, sealed well, then transferred to an oven, and heated to 200°C for 24 hours. After the reaction, the reaction kettle was lowered to room temperature, and the obtained hollow porous ZnO was separated by centrifugation (6000rpm centrifugation for 7min), washed 5 times with deionized water, and dried at 40°C for one day by vacuum drying. The hollow porous nanometer ZnO powder is obtained. The prepared hollow porous ZnO nanoparticles have an outer diameter of 510 nm.

For the process route of kneading and extruding into a tube, refer to Example 2 to obtain a lightweight and antibacterial electronic cigarette casing.

Example 11:

Take 0.5g cross-linked polyacrylic acid PAA (particle size is 150nm, cross-linking degree is 25%) as a template, disperse in 200mL deionized water, finally add ZnCl ₂ 0.8g and urea 1.6g, and stir evenly to make it completely Dissolve in water. The entire system was transferred to a tetrafluoroethylene liner (volume 300 mL) of a stainless steel autoclave, sealed well, then transferred to an oven, and heated to 120°C for 24 hours. After the reaction, the reaction kettle was lowered to room temperature, and the obtained hollow porous ZnO was separated by centrifugation (8000rpm centrifugation for 7min), washed 4 times with deionized water, and dried at 50°C for one day by vacuum drying. The hollow porous nanometer ZnO powder is obtained. The prepared hollow porous ZnO nanoparticles have an outer diameter of 800 nm.

For the process route of kneading and extruding into a tube, refer to Example 2 to obtain a lightweight and antibacterial electronic cigarette casing.

Example 12:

Use 0.5g of cross-linked polyacrylic acid PAA (particle size: 150nm, cross-linking degree: 25%) as a template, disperse in 200mL of deionized water, finally add ZnCl ₂ 1.0g and urea 2.0g, and stir evenly to make it completely Dissolve in water. The whole system was transferred to the tetrafluoroethylene liner (volume 300mL) of a stainless steel autoclave, sealed well, then transferred to an oven, and heated to 160°C for 20 hours. After the reaction, the reaction kettle was lowered to room temperature, and the obtained hollow porous ZnO was separated by centrifugation (8000rpm centrifugation for 7min), washed three times with deionized water, and dried at 60°C for one day by vacuum drying. The hollow porous nanometer ZnO powder is obtained. The prepared hollow porous ZnO nanoparticles have an outer diameter of 1200nm.

For the process route of kneading and extruding into a tube, refer to Example 2 to obtain a lightweight and antibacterial electronic cigarette casing.

Example 13:

With 0.5g cross-linked polyacrylic acid PAA (particle size is 150nm, cross-linking degree is 25%) as template, dispersed in the middle of 200mL deionized water, finally add ZnCl ₂ 0.5g and hexamethylene tetraammonium 1.0g, and Stir well to completely dissolve in water. The entire system was transferred to a tetrafluoroethylene liner (volume 300 mL) of a stainless steel autoclave, sealed well, then transferred to an oven, and heated to 200°C for 12 hours. After the reaction, the reaction kettle was lowered to room temperature, and the obtained hollow porous ZnO was separated by centrifugation (8000rpm centrifugation for 7min), washed 5 times with deionized water, and dried at 60°C for one day by vacuum drying. The hollow porous nanometer ZnO powder is obtained. The prepared hollow porous ZnO nanoparticles have an outer diameter of 630 nm.

For the process route of kneading and extruding into a tube, refer to Example 2 to obtain a lightweight and antibacterial electronic cigarette casing.

Example 14:

Use 0.5g of cross-linked polyacrylic acid PAA (particle size: 150nm, cross-linking degree: 25%) as a template, disperse in 200mL of deionized water, finally add 0.5g of ZnCl ₂ and 1.0g of ethanolamine, and stir evenly to make it completely Dissolve in water. The whole system was transferred to the tetrafluoroethylene liner (volume 300mL) of a stainless steel autoclave, sealed well, then transferred to an oven, and heated to 200°C for 36 hours. After the reaction, the reaction kettle was lowered to room temperature, and the obtained hollow porous ZnO was separated by centrifugation (8000rpm centrifugation for 7min), washed with deionized water for 3 to 5 times, and dried at 60°C by vacuum drying. One day, the hollow porous nanometer ZnO powder was obtained. The prepared hollow porous ZnO nanoparticles have an outer diameter of 480 nm.

For the process route of kneading and extruding into a tube, refer to Example 2 to obtain a lightweight and antibacterial electronic cigarette casing.

Example 15:

Take 0.5g cross-linked polyacrylic acid PMAA (particle size is 150nm, cross-linking degree is 25%) as a template, disperse in 200mL deionized water, finally add ZnCl ₂ 0.5g and urea 1.0g, and stir evenly to make it completely Dissolve in water. The whole system was transferred to the tetrafluoroethylene liner (volume 300mL) of a stainless steel autoclave, sealed well, then transferred to an oven, and heated to 120°C for 36 hours. After the reaction, the reaction kettle was lowered to room temperature, and the obtained hollow porous ZnO was separated by centrifugation (8000rpm centrifugation for 7min), washed 5 times with deionized water, and dried at 60°C for one day by vacuum drying. The hollow porous nanometer ZnO powder is obtained. The prepared hollow porous ZnO nanoparticles have an outer diameter of 540 nm.

For the process route of kneading and extruding into a tube, refer to Example 2 to obtain a lightweight and antibacterial electronic cigarette casing.

Claims (10)

1. A lightweight antibacterial electronic cigarette case, characterized in that the preparation method of the electronic cigarette case comprises the steps: Step 1, disperse 0.1 to 5 parts by weight of crosslinked polyacrylic acid PAA or crosslinked polymethacrylic acid PMAA in 25 to 500 parts by weight of deionized water, add 0.1 to 2.5 parts by weight of soluble zinc salt and 0.4 ~8 parts by weight of amine compounds were stirred and dissolved to obtain a reaction system; the reaction system was transferred to a stainless steel high-pressure reactor, sealed and then transferred to an oven, and reacted at 120-200 ° C for 12-36 hours; Cool down to room temperature, centrifuge at 5000-12000rpm for 2-10 minutes, separate hollow porous ZnO, wash with deionized water 3-5 times, dry at 40-60°C for 24h, and obtain hollow porous nano-ZnO powder; Step 2, 1-5 parts by weight of porous hollow nano-ZnO powder, 80-100 parts by weight of polymer masterbatch, 5-10 parts by weight of modification aid, 1-3 parts by weight of calcium carbonate and 1-4 parts by weight of The foaming agent is added to the kneader, heated and kneaded for 1 to 5 hours, then added to the mixer, and injected into the tubular mold quickly under high pressure; under the conditions of molding pressure of 2 to 7MPa and temperature of 50 to 80°C, the low pressure foaming method is adopted. The polymer melt is foamed and molded; the molded shell is cooled and released from the mold, dried and then cut to obtain a light and antibacterial electronic cigarette shell. 2. The light-weight antibacterial electronic cigarette case according to claim 1, characterized in that, in the preparation method of the electronic cigarette case, the cross-linked PAA or cross-linked PMAA is prepared by distillation precipitation polymerization ; The cross-linking agent used is a bis-vinylbisacrylamide cross-linking agent, a bis-vinyl diester cross-linking agent or a bis-vinylbenzene cross-linking agent. 3. The light antibacterial electronic cigarette case according to claim 1, characterized in that, in the preparation method of the electronic cigarette case, the particles of the cross-linked polyacrylic acid PAA or the cross-linked polymethacrylic acid PMAA The diameter is 50-500nm, and the degree of cross-linking is 10%-50%. 4. The lightweight antibacterial electronic cigarette casing according to claim 1, characterized in that, in the preparation method of the electronic cigarette casing, the soluble zinc salt in step 1 is ZnCl ₂ , Zn(NO3) ₂ , ZnSO ₄ or Zinc acetate. 5. The lightweight antibacterial electronic cigarette casing according to claim 1, wherein in the preparation method of the electronic cigarette casing, the amine compound in step 1 is selected from urea, hexamethylenetetramine, ethanolamine, Diethanolamine and melamine. 6. The lightweight antibacterial electronic cigarette casing according to claim 1, wherein in the preparation method of the electronic cigarette casing, the polymer masterbatch in step 2 is PC resin, ABS resin or a mixture of both. 7. The light-weight antibacterial electronic cigarette casing according to claim 1, characterized in that, in the preparation method of the electronic cigarette casing, the modification auxiliary agent in step 2 consists of 5-20 parts by weight of antioxidant, 0-30 parts by weight of foaming aid and 20-80 parts by weight of toughening agent, wherein the toughening agent is one or a mixture of SBS, SEBS and EVA; the foaming aid is _TiO2 or A mixture of TiO ₂ and ZnO; antioxidants are quinoline derivatives and phosphite derivatives. 8. The lightweight antibacterial electronic cigarette case according to claim 1, characterized in that: the foaming agent in step 2 is one of azo compounds, nitroso compounds and sodium carbonate salts through a polymer carrier Resin-encapsulated masterbatch balls. 9. The method for preparing the light-weight antibacterial electronic cigarette casing according to any one of claims 1-8, characterized in that it comprises the following steps: (1) Use 0.1-5g of cross-linked polyacrylic acid PAA or cross-linked polymethacrylic acid PMAA as a template, disperse in 25-500mL of deionized water, and finally add 0.1-2.5g of soluble zinc salt and 0.4- 8g, and stir evenly to dissolve it completely in water; transfer the whole system to the tetrafluoroethylene lining of a stainless steel autoclave with a volume of 50-750mL, seal it well, transfer it to an oven, and heat it to 120-200°C to keep 12 to 36 hours; after the reaction, lower the reaction kettle to room temperature, separate the obtained hollow porous ZnO by centrifugation, wash with deionized water for 3 to 5 times, and vacuum dry at 40 to 60°C After drying for one day, the hollow porous nano-ZnO powder was obtained; (2) Add 80 to 100 parts of polymer masterbatch, 5 to 10 parts of modifying additives, 1 to 5 parts of porous hollow nano-ZnO powder, 1 to 3 parts of calcium carbonate and 1 to 4 parts of foaming agent to knead After heating and kneading by the machine for 1-5 hours, add it to the mixer; inject it into the tubular mold through high-pressure rapid injection in the mixer, and use the low-pressure foaming method at a molding pressure of 2-7MPa and a temperature of 50-80°C Foam molding is performed on the polymer melt; finally, the molded shell is cooled and released from the mold, and a foamed aseptic tube is obtained after drying; after the tube is cut, a light antibacterial electronic cigarette shell can be obtained. 10. The preparation method of the light-weight antibacterial electronic cigarette casing as claimed in claim 9, characterized in that, in step (1): Use cross-linked polymethacrylic acid PMAA as a template; the cross-linking agent used is selected from bis-vinyl bis-acrylamides, bis-vinyl diesters and bis-vinyl benzenes; the particle size of PMAA is 50-500nm, The degree of cross-linking is 10% to 50%; The soluble zinc salt is selected from ZnCl ₂ , Zn(NO3) ₂ , ZnSO ₄ and zinc acetate; Amines are selected from urea, hexamethylenetetramine, ethanolamine, diethanolamine and melamine; The particle size of the obtained hollow porous ZnO nanoparticles is in the range of 200-2000nm; The centrifugal speed is 5000～12000rpm; In step (2): the polymer master batch is one or both of PC resin and ABS resin; Modification aids are antioxidants, foaming aids and toughening agents, wherein the toughening agent is one or a mixture of SBS, SEBS and EVA; foaming aids are TiO ₂ and ZnO and TiO ₂ mixture; The foaming agent is one of azo compounds, nitroso compounds and sodium carbonate salts encapsulated by a polymer carrier resin.